Manufacture of compositions of matter containing synthetic resins



Patented Mar. 9, 1937 UNITED STATES PATENT OFFICE hereas or comosmons orMATTER com'smmc I srnrmmc RESINS William Henry Moss, London, England,assignor to Celanese Corporation of America, a corporation of DelawareNo Drawing. Original application November 10, 1934, Serial No. 752,473.Divided and this a? plication March 19, 1936, Serial No. 69,663. InGreat Britain November 22, 1933 9 Claims. (01. 134-26) This inventionrelates to the manufacture of lacquers, moulding powders andothercompositions of .matter containing synthetic resins and to theproduction of films and other spun products, moulded articles and thelike from such compositions of matter, and is a divisional applicationof my U. S. application S. No. 152,473 I filed November 10, 1934.

Dimculties have been experienced in the past in the manufacture oflacquers and other coating compositions containing synthetic resins, e.g. lacquers containing phenol formaldehyde resins, in that suchcompositions and films formed therefrom have tended to darken onexposure to light.

- It has now been discovered that lacquers and like compositions whichhave a much reduced tendency to darken on exposure to light may beformed from synthetic resins obtainable by reacting a phenol with ahalogenated aliphatic. ketone and then reacting the product withformaldehyde or a substance yielding formaldehyde. Furthermore in themanufacture of moulded 'articles from compositions containing syntheticresins in which conversion of a fusible resin to an infusible for-moccurs, it is desirable that such conversion shall, take place asrapidly as possible. It has been found that the synthetic resinsreferred to above are particularly rapidly converted into an insoluble,infusible form so that moulding compositions containing them are ofconsiderable value.

The present invention, therefore, is concerned with lacquers, mouldingpowders and other com positions of matter which comprise resinsobtainable by reacting a phenol with a halogenated aliphatic ketone andthen reacting the product with formaldehyde or a substance yieldingformaldehyde, and with the production of films and other spun products,moulded articles and the like therefrom.

The phenols employed in the manufacture of the synthetic resins employedaccording to the present invention are preferably monohydrlc' phenols,e. g. xylenols and metaand para-cresols, and poly-nuclear compoundswhich, though more than one phenolic group is present, do not containmore than one such group in each nucleus. Partlcularly valuable 'phenolsare phenol itself,

o-cresol, the mixture of cresols known as cresylic 0 acid, anddiphenylol propane. The best halogenated ketone to employ is'chloracetone, though other halogenated ketones, e. g. monochlor methylethyl ketone may be employed. Instead of formaldehyde itself, substancesyielding formaldehyth, e. g. hexametbrlenc tetramine may be obtainedfrom a phenol and a ketone may be reacted with formaldehyde to form aresin of the type to which the present invention relates. Thuscondensation products obtained from aphenol and chloracetone are alreadyknown, and the resins employed according to the present invention may beobtained by reacting such products with formaldehyde; The proportions ofconstituents employed may be varied, but in genphenol to one molecule ofketone and from one to three molecules of formaldehyde yield the bestresults. When an acid catalyst is to be employed in a reaction in whichhexamethylene tetramine is present, due allowance should of course bemade for the acid neutralized in decomposing the hexamethylenetetramine.

In general, the synthetlcresins employed in the compositions of matterof this invention are fusible, soluble in solvents. such as acetone,alcohol, acetic acid and dilute caustic soda, and are insoluble inbenzene and similar hydrocarbons. The synthetic resins employedaccording .to this invention may be rapidly converted into an infusibleinsoluble form and for this reason compositions comprising such resinsare very valuable forthe production of moulded products,

e. g. gramophone records. The synthetic resins have a very goodresistance to light, and films may be formed from compositionscontaining the above synthetic resins and cellulose acetate which showpractically no darkening after an exposure of four days to thefadeometer, (whereas ordinary phenol-formaldehyde resins showconsiderable darkening under these conditions) which is of course aproperty of great value in lacquers. The-synthetic resins referred toabove when prepared .in the presence. of acid catalysts are, in general,compatible with cellulose acetate and other organic derivatives ofcellulose. The

resins are also compatible with other natural and synthetic resinl.particuhl'ly with the synthetic eral proportions of about two moleculesof the resins obtained by the polymerization of vinyl acetate or othervinyl compounds, and the compositions of the present invention maycontain, in addition to the synthetic resins, any of such substances ormixtures thereof. Compositions containing the above synthetic resinsdissolved in organic solvents such as acetone may be formed into filmsand other products by wet or dry spinning processes. As stated above,the resins obtained from chloracetone, formaldehyde and phenol,o-cresol, cresylic acid or diphenylol propane are especially valuable.

The compositions of the present invention may contain suitableplasticizers, examples of which are tricresyl and triphenyl phosphatesand other alkyl phosphates, di-ethyl and di-butyl tartrates and otheresters, for example diand tri-acetins. They may also contain colouringmaterials, e. g. boneblack, iron oxide and manganese dioxide. andfillers, for example China clay, micro asbestos, bentonite, wood flour,cotton fiock, mica and gypsum.

The following examples are given in order to illustrate the invention,but it is to be understood that they do not limit it in any way:-

Example 1 The following is an example of one method of preparing asynthetic resin which may be employed in the compositions of matter ofthe present invention. 50 parts by weight of phenolchloracetone resinare heated at 100 C. under reflux for about 5 minutes "with 20-40 partsby weight of 40% formaldehyde solution in the presence of about .5 partsby weight of concentrated hydrochloric acid. The resin formed is washedwith water and is similar in appearance to the phenol-chloracetone resinexcept that it has a lower melting point. dried it is fusible at about100 C., while on cooling it shows a melting point of approximately 0.,whereas the phenol-chloracetone resin employed as starting materialsolidifies at about 120 C. Moreover, while the phenol-chloracetone resinmay be heated for a considerable time at temperatures up to 200 C.without being converted into an insoluble form, the phenol-chloracetoneformaldehyde resin may be converted into such form by heating attemperatures'of even of the order of C. This property of course is ofgreat importance in the manufacture of moulded products. The resin issoluble in acetone, acetic acid, and dilute caustic soda, and insolublein benzole, and is compatible with cellulose acetate in all proportionsgiving hard films.

The process described in the above example may be modified by the use ofabout .25 parts by weight of phosphoric acid instead of the hydrochlcricacid. In this case the reaction is considerably slower, taking from 2-4hours, and in consequence may be better controlled. If, instead ofphosphoric acid an alkaline catalyst is used, for example 2 parts byweight of 5% caustic soda solution, the resin obtained is incompatiblewith cellulose acetate.

Example 2 108 parts by weight of ortho-cresol are heated under refluxwith 46 parts by weight of chloracetone in the presence of 10 parts byweight of concentrated hydrochloric acid. A vigorous reobtained, whichwhenpuriflerl melts at about When washed and Dibutyl tartrate A clearcoating lacquer may be prepared from the following constitutents:-

I Parts by weight Cellulose acetate 40 Phenol-chloracetone formaldehyderesin 60 Diethyl phthalate 20 Tricresyl phosphate 5 Acetone 200Benzene"; 112, Alcohol 8B Ethyl lactate 40 Example 4 A pigmented lacquermaybe obtained by incorporating 20 parts by weight of chrome green or 10parts by weight of carbon black in. the lacquer described in Example 3.g

Example 5 A composition containing vinyl acetate and the synthetic resinmay be obtained from the following constituents:

, Parts by weight 'Polymerized vinyl acetate 50 Phenol-chloracetoneformaldehyde resin"..- 50 Acetone 200 Benzene 112 Alcohol 88 Instead ofvinyl acetate, ethyl cellulose, benzyl cellulose or cellulose nitratemay be employed.

Example 6 A plastic composition containing the resin may be obtained asfollows:-

Parts by weight 100 The dibutyl tartrate and resin are incorporated inany suitable manner with the cellulose acetate, either with or withoutthe use of solvents. The resulting mass may be ground to a line powder,suitable for moulding,

The above composition may also contain a filler, e. g. china clay, microasbestos or bentonite.

Example 7 Cellulose ace Phenol-chloracetone formaldehyde resin A productcontaining a large amount of resin is prepared fromthefollowingconstituents:-

I Parts by weight Instead of the phenol-chloracetone formaldehyde resinthe resin obtained from ortho-cresol according to Example 2 may beemployed in corresponding proportions in Examples 3-7.

Having described my invention what 1 deslle'td secure by Letters Patentis:-'-

, 1,. Compositions of matter containing an organic derivative ofcellulose and a synthetic resin compatible therewith and obtainable bythe reaction of formaldehyde with the condensation product of a phenolwith a halogenated aliphatic ketone.

2. Compositions of matter containing-cellulose acetate and a syntheticresin compatible therewith and obtainable by the reaction offormaldehvde with the condensation product 0! phenol itself withchloracetone.

- 5. Lacquers and other coating compositions containing an organicderivative oi cellulose and a synthetic resin, compatible therewith andobtalmble bythereaction of formaldehyde with the condensation product ofaphenol with chloracetone, dissolved in a solvent medium. a

6,,1iacquers and other coating compositions containing cellulose acetateanda synthetic resin, compatible therewith and obtainable by thereaction 0! formaldehyde with the condensation product of a phenol withchloracetone; dissolved in a solvent medium. 7

I. Moulding compositions containing an or ganic derivative of celluloseand a synthetic resin compatible therewith and obtainable by thereaction 0! formaldehyde with the condensation product of a phenol withchloracetone.

8. Holding compositions containing cellulose acetate and a syntheticresin compatible there- I with and obtainable by the reaction ofioi'mall'lehyde with the condensation product of a phenol withchloracetone.

9. Gramophone records and other moulded products comprising an organicderivative oi cellulose and a synthetic resin compatible there with andobtainable by the reaction of formaldehyde with the condensation productof a phenol with a halogenated aliphatic ketone.

HENRY MOS S.

